Heteroatom doping effectively tunes the electronic conductivity of transition metal selenides (TMSs) with rapid K+ accessibility in potassium ion batteries (PIBs). Although considerable efforts are dedicated to investigating the relationship between the doping strategy and the resulting electrochemistry, the doping mechanisms, especially in view of the ion and electronic diffusion kinetics upon cycling, are seldom elucidated systematically. Herein, the crystal structure stability, charge/ion state, and bandgap of the active materials are found to be precisely modulated by favorable heteroatom doping, resulting in intrinsically fast kinetics of the electrode materials. Based on the combined mechanisms of intercalation and conversion reactions, electron and K+ ion transfer in Ni‐doped CoSe2 embedded in carbon nanocomposites (Ni‐CoSe2@NC) can be significantly enhanced via electronic engineering. Benefiting from the synthetic controlled Ni grains, the heterointerface formed by the intermediate products of electrochemical reactions in Ni‐CoSe2@NC strengthens the conversion kinetics and interdiffusion process, developing a low‐barrier mesophase with optimized potassium storage. Overall, an electronic tuning strategy can offer deeper atomic insights into the conversion reaction of TMSs in PIBs.